JP4862248B2 - Organic electroluminescence element, lighting device and display device - Google Patents

Description

  The present invention relates to an organic electroluminescence element, a lighting device, and a display device.

  Conventionally, there is an electroluminescence display (ELD) as a light-emitting electronic display device. Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL element has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode. By injecting electrons and holes into the light emitting layer and recombining them, excitons (exciton) are obtained. Is a device that emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several V to several tens of V, and further self-emission. Since it is a type, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving, portability, and the like.

  For the development of organic EL elements for practical use in the future, organic EL elements that emit light efficiently and with high brightness with lower power consumption are desired. For example, stilbene derivatives, distyrylarylene derivatives, or tris A technique for doping a styrylarylene derivative with a small amount of a phosphor to improve emission luminance and extend the lifetime of the device (see, for example, Patent Document 1), and 8-hydroxyquinoline aluminum complex as a host compound. A device having an organic light-emitting layer doped with a trace amount of phosphor (for example, see Patent Document 2), a device having an organic light-emitting layer doped with a quinacridone dye as a host compound using 8-hydroxyquinoline aluminum complex (for example, , See Patent Document 3).

  In the technique disclosed in the above-mentioned patent document, when the emission from the excited singlet is used, the generation ratio of the singlet exciton and the triplet exciton is 1: 3, so the generation probability of the luminescent excited species is 25%. Since the light extraction efficiency is about 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University has reported on organic EL devices that use phosphorescence from excited triplets (see, for example, Non-Patent Document 1), research on materials that exhibit phosphorescence at room temperature has become active. (For example, refer nonpatent literature 2 and patent literature 4.).

  When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so in principle the luminous efficiency is four times that of excited singlets, and the performance is almost the same as that of cold cathode tubes. It can be applied to and attracts attention. For example, many compounds have been studied for synthesis centering on heavy metal complexes such as iridium complexes (see, for example, Non-Patent Document 3).

  Further, studies using tris (2-phenylpyridine) iridium as a dopant have been made (see, for example, Non-Patent Document 2).

In addition, L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac) (see, for example, Non-Patent Document 4) as a dopant, and tris (2- (p-tolyl) pyridine) iridium (as a dopant) Studies using Ir (ptpy) ₃ ), tris (benzo [h] quinoline) iridium (Ir (bzq) ₃ ), Ir (bzq) ₂ ClP (Bu) _3, etc. (for example, see Non-Patent Document 5). Has been done.

  In order to obtain high luminous efficiency, a hole transporting compound is used as a host of the phosphorescent compound (see, for example, Non-Patent Document 6).

  Further, various electron transporting materials are used as phosphorescent compound hosts by doping them with a novel iridium complex (see, for example, Non-Patent Document 4). Furthermore, high luminous efficiency is obtained by introducing a hole blocking layer (see, for example, Non-Patent Document 5).

  Further, a thermally stable hole transport material that includes a partial structure of a nitrogen-containing aromatic ring compound and extends in three or four directions around a nitrogen atom or aryl is disclosed ( (See Patent Document 5). However, Patent Document 5 does not disclose any phosphorescent organic EL element.

  Further, a light-emitting material that is a nitrogen-containing aromatic ring compound and has high luminance is disclosed (see Patent Document 6). However, Patent Document 6 does not disclose any phosphorescent organic EL element.

Currently, further improvement in light emission efficiency and long life of organic EL devices using phosphorescence emission are being studied, but the green light emission has achieved an external extraction efficiency of nearly 20%, which is the theoretical limit. However, only the low current region (low luminance region) is present, and the theoretical limit has not yet been achieved in the high current region (high luminance region). Furthermore, sufficient efficiency has not yet been obtained for other luminescent colors, and improvements are required. In addition, organic EL devices for practical use in the future will emit light efficiently and with high brightness. Development of the organic EL element which does is desired. Particularly, there is a demand for an element that emits light with high efficiency in an organic EL element that emits blue phosphorescence.
Japanese Patent No. 3093796 Japanese Unexamined Patent Publication No. 63-264692 JP-A-3-255190 US Pat. No. 6,097,147 Japanese Patent Publication No.7-110940 JP 2001-160488 A M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) M.M. E. Thompson et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu) Moon-Jae Youn. 0 g, Tsutsuo Tsutsui et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu) Ikai et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu)

  An object of the present invention is to provide an organic electroluminescence element, a lighting device, and a display device that have a high external extraction yield and a long lifetime.

The above object of the present invention has been achieved by the following configurations 1 to 25 .

1. In the organic electroluminescence device having at least a light emitting layer and a hole blocking layer as a constituent layer,
The hole blocking layer contains a compound represented by the following general formula (1), and the light emitting layer is at least one selected from the group of compounds consisting of the following general formula (B) or general formula (C). An organic electroluminescence device comprising a seed compound.

[ Wherein , Z ₁ represents a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring or triazine ring , Z ₂ represents a benzene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring or triazine ring , and Z ₃ represents It represents —CH ₂ —, —O— , —S— or a simple bond. R ₁₀₁ represents a hydrogen atom or a substituent. ]

[In the formula, Ar ₃₁ and Ar ₃₂ each represent an arylene group or a divalent heterocyclic group, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a substituent, and L ₃ represents a divalent linkage. Represents a group, a trivalent linking group or a single bond. n31, n32, n33, and n34 each represent an integer of 0 to 4, and n3 represents 1 or 2. However, the compound shown below is excluded from the compound represented by the general formula (B). ]

[Wherein, Ra to Rg each represents a hydrogen atom or a substituent, and the substituents represented by Ra to Rg may be the same or different. m represents an integer of 1 to 3, and n represents an integer of 0 to 2. However, the compound shown below is remove | excluded from the compound represented by this general formula (C). ]

2. In the general formula (1) , Z ₁ represents a pyridine ring, Z ₂ represents a benzene ring or a pyridine ring, Z ₃ represents a simple bond, and the light emitting layer is composed of the general formula (B). 2. The organic electroluminescence device as described in 1 above , which contains at least one compound selected from the group of compounds .

3. 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (1-3).

[Wherein, R _{521 to} R ₅₂₇ each independently represents a hydrogen atom or a substituent. ]
4). 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (1-4).

[Wherein, R _{531 to} R ₅₃₇ each independently represents a hydrogen atom or a substituent. ]
5. 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (1-5).

[Wherein, R _{541 to} R ₅₄₈ each independently represents a hydrogen atom or a substituent. ]
6). 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (1-6).

[In the formula, R ₅₅₁ ~ R ₅₅₈ Each independently represents a hydrogen atom or a substituent. ]

7). 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (1-9).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ]
8). 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (1-10).

  [Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ]

9. 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (3).

[Wherein, R _{601 to} R ₆₀₆ each independently represents a hydrogen atom or a substituent, and at least one of R _{601 to} R ₆₀₆ is represented by Formulas (2-1) to (2-4). R _{502 to} R ₅₀₇ , R _{512 to} R ₅₁₇ , R _{522 to} R ₅₂₇ , R _{532 to} R ₅₃₇ each independently represents a hydrogen atom or a substituent, The substituents may be the same or different. ]
10. 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (4).

[Wherein, R _{611 to} R ₆₂₀ each independently represent a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ represents the general formulas (2-1) to (2 -4) represents at least one group selected from the groups represented by ]

11. 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (7).

[Wherein, R _{651 to} R ₆₅₆ each independently represents a hydrogen atom or a substituent, and at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2 -4) represents at least one group selected from the groups represented by na represents an integer of 0 to 5, and nb represents an integer of 1 to 6, but the sum of na and nb is 6. ]

12 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (10).

[Wherein, R _{691 to} R ₇₀₀ each independently represents a hydrogen atom or a substituent, and L ₁ represents a divalent linking group. At least one of R _{691 to} R ₇₀₀ represents at least one group selected from the groups represented by formulas (2-1) to (2-4) described in 9 above . ]
13. 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (11).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
14 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (12).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
15. 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (13).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
16. 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (14).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ]
17. 3. The organic electroluminescence device as described in 1 or 2 above, wherein the compound represented by the general formula (1) is represented by the following general formula (15).

[Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom. ]
18. 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (16).

[Wherein, o and p each represent an integer of 1 to 3, and Ar ₁ and Ar ₂ each represent an arylene group or a divalent aromatic heterocyclic group. Z ₁ and Z ₂ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group. ]
19. 3. The organic electroluminescence device according to 1 or 2 , wherein the compound represented by the general formula (1) is represented by the following general formula (17).

[Wherein, o and p each represent an integer of 1 to 3, and Ar ₁ and Ar ₂ each represent a divalent arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represents a 6-membered aromatic heterocyclic ring containing at least one nitrogen atom, and L represents a divalent linking group. ]
20. The phosphorescent light-emitting layer as the constituent layer, and the phosphorescent light-emitting layer contains the compound represented by the general formula (1), according to any one of 1 to 19 above Organic electroluminescence device.

21. 21. A display device comprising the organic electroluminescence element according to any one of 1 to 20 above .

22. The organic electroluminescence device according to any one of 1 to 21 , wherein the light emission is white.

23. 23. A display device comprising the organic electroluminescence element as described in 22 above .

24. 23. An illuminating device comprising the organic electroluminescence element as described in 22 above .

25. 25. A display device comprising the lighting device according to 24 and a liquid crystal element as display means.

  According to the present invention, an organic electroluminescence element, a lighting device, and a display device that have a high external extraction yield and a long lifetime can be provided.

  In the organic electroluminescence device of the present invention (hereinafter also referred to as organic EL device), the external extraction yield is high by adopting the configuration defined in any one of claims 1 to 33 or 35. An organic EL device having a long life could be obtained.

  Moreover, it was possible to obtain a high-luminance and long-life lighting device and display device using the organic EL element exhibiting the above characteristics.

  Hereinafter, details of each component according to the present invention will be sequentially described.

  As a result of intensive studies, the inventors include the compound represented by the general formula (1) in a hole blocking layer described later, and the light emitting layer described later includes the general formulas (A) to (D). It has been found that an organic EL device prepared so as to contain at least one compound selected from the compound group consisting of) has high luminous efficiency and can have a long lifetime.

<< Compound Represented by Formula (1) >>
The compound represented by the general formula (1) according to the present invention will be described.

In the general formula (1), Z ₁ represents an aromatic heterocyclic ring which may have a substituent, and Z ₂ represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring which may have a substituent. , Z ₃ represents a divalent linking group or a simple bond. R ₁₀₁ represents a hydrogen atom or a substituent.

In the general formula (1), examples of the aromatic heterocycle represented by Z ₁ and Z ₂ include a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, Diazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, diazacarbazole ring (It represents a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom). Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁₀₁ described later.

In the general formula (1), examples of the aromatic hydrocarbon ring represented by Z ₂ include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene. Ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene Ring, pyranthrene ring, anthraanthrene ring and the like. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁₀₁ described later.

In the general formula (1), examples of the substituent represented by R ₁₀₁ include an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group). Group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.) Etc.), aryl groups (eg phenyl group, naphthyl group etc.), aromatic heterocyclic groups (eg furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group) , Thiazolyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg Pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cyclo An alkoxyl group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), an aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, Octylthio group, dodecylthio group etc.), cycloalkylthio group (eg cyclopentylthio group, cyclohexylthio group etc.), arylthio group (eg phenylthio group, naphthylthio group etc.), alkoxycarbonyl group (eg meso Ruoxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, Aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclyl group) Hexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group) Octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonyl) Amino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthy Carbonylamino group, etc.), carbamoyl group (eg, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylamino) Carbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group) , Dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethyl) Rufinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group) , Butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (for example, amino group, ethyl group) Amino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridy Amino groups, etc.), halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, etc.), fluorinated hydrocarbon groups (eg, fluoromethyl groups, trifluoromethyl groups, pentafluoroethyl groups, pentafluorophenyl groups, etc.), And cyano group, nitro group, hydroxyl group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.).

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

  Preferred substituents are an alkyl group, a cycloalkyl group, a fluorinated hydrocarbon group, an aryl group, and an aromatic heterocyclic group.

  As the divalent linking group, in addition to hydrocarbon groups such as alkylene, alkenylene, alkynylene, and arylene, those containing a hetero atom may be used, and a thiophene-2,5-diyl group, pyrazine-2, It may be a divalent linking group derived from a compound having an aromatic heterocyclic ring (also called a heteroaromatic compound) such as a 3-diyl group, or may be a chalcogen atom such as oxygen or sulfur. . Further, it may be a group such as an alkylimino group, a dialkylsilanediyl group, or a diarylgermandiyl group that connects and connects heteroatoms.

  A mere bond is a bond that directly bonds the connecting substituents together.

In the present invention, Z _{1 in the} general formula (1) is preferably a 6-membered ring. Thereby, luminous efficiency can be made higher. Furthermore, the lifetime can be further increased.

In the present invention, it is preferable that the Z ₂ in the general formula (1) is a 6-membered ring. Thereby, luminous efficiency can be made higher. Furthermore, the lifetime can be further increased.

Furthermore, it is preferable that Z ₁ and Z _{2 in} the general formula (1) are both 6-membered rings because the luminous efficiency can be further increased. Furthermore, it is preferable because the lifetime can be further increased.

  Preferred among the compounds represented by the general formula (1) are compounds represented by the general formulas (1-1) to (1-13).

In the general formula (1-1), R _{501 to} R ₅₀₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-1), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-2), R _{511 to} R ₅₁₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-2), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-3), R _{521 to} R ₅₂₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-3), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-4), R _{531 to} R ₅₃₇ each independently represents a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-4), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In Formula (1-5), R ₅₄₁ ~R ₅₄₈ each independently represents a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-5), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-6), R _{551 to} R ₅₅₈ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-6), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-7), R _{561 to} R ₅₆₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-7), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (1-8), R _{571 to} R ₅₇₇ each independently represent a hydrogen atom or a substituent.

  By using the compound represented by the general formula (1-8), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

  In the general formula (1-9), R represents a hydrogen atom or a substituent. The plurality of R may be the same or different.

  By using the compound represented by the said General formula (1-9), it can be set as an organic electroluminescent element with higher luminous efficiency. Furthermore, it can be set as a longer life organic EL element.

  In the general formula (1-10), R represents a hydrogen atom or a substituent. The plurality of R may be the same or different.

  By using the compound represented by the general formula (1-10), an organic EL device with higher luminous efficiency can be obtained. Furthermore, a long-life organic EL element can be obtained.

In addition, the compound represented by the general formula (1) is preferably a compound having at least one group represented by any one of the general formulas (2-1) to (2-8). In particular, it is more preferable to have 2 to 4 groups represented by any one of the general formulas (2-1) to (2-8) in the molecule. In this case, the structure represented by the general formula (1) includes a case where the portion excluding R ₁₀₁ is replaced by the general formulas (2-1) to (2-8).

  At this time, the compounds represented by the general formulas (3) to (17) are particularly preferable for obtaining the effects of the present invention.

In the general formula (3), R _{601 to} R ₆₀₆ represent a hydrogen atom or a substituent, and at least one of R _{601 to} R ₆₀₆ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (3), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (4), R _{611 to} R ₆₂₀ represent a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (4), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (5), R _{621 to} R ₆₂₃ represent a hydrogen atom or a substituent, and at least one of R _{611 to} R ₆₂₀ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (5), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (6), R _{631 to} R ₆₄₅ represent a hydrogen atom or a substituent, and at least one of R _{631 to} R ₆₄₅ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (6), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (7), R _{651 to} R ₆₅₆ represent a hydrogen atom or a substituent, and at least one of R _{651 to} R ₆₅₆ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented. na represents an integer of 0 to 5, and nb represents an integer of 1 to 6, but the sum of na and nb is 6.

  By using the compound represented by the general formula (7), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (8), R _{661 to} R _{672 each} represents a hydrogen atom or a substituent, and at least one of R _{661 to} R ₆₇₂ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (8), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (9), R _{681 to} R ₆₈₈ represent a hydrogen atom or a substituent, and at least one of R _{681 to} R ₆₈₈ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

  By using the compound represented by the general formula (9), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the general formula (10), R _{691 to} R ₇₀₀ represent a hydrogen atom or a substituent, and at least one of R _{691 to} R ₇₀₀ is represented by the general formulas (2-1) to (2-4). The group represented by either is represented.

In the general formula (10), the divalent linking group represented by L ₁ is an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene). Group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.) ), Cyclopentylene group (eg, 1,5-cyclopentanediyl group, etc.), alkenylene group (eg, vinylene group, propenylene group, etc.), alkynylene group (eg, ethynylene group, 3-pentynylene group, etc.), In addition to hydrocarbon groups such as arylene groups, groups containing heteroatoms (eg, —O , -S- and the like, a divalent group containing a chalcogen atom, -N (R)-group, wherein R represents a hydrogen atom or an alkyl group, and the alkyl group in the general formula (1), And the same as the alkyl group represented by R ₁₀₁ .

  In each of the alkylene group, alkenylene group, alkynylene group, and arylene group, at least one of carbon atoms constituting the divalent linking group is a chalcogen atom (oxygen, sulfur, etc.) or -N (R). -It may be substituted with a group or the like.

Furthermore, as the divalent linking group represented by L ₁ , for example, a group having a divalent heterocyclic group is used. For example, an oxazolediyl group, a pyrimidinediyl group, a pyridazinediyl group, a pyrandiyl group, a pyrrolindiyl group. Group, imidazoline diyl group, imidazolidine diyl group, pyrazolidine diyl group, pyrazoline diyl group, piperidine diyl group, piperazine diyl group, morpholine diyl group, quinuclidine diyl group and the like, and thiophene-2,5- A divalent linking group derived from a compound having an aromatic heterocyclic ring (also referred to as a heteroaromatic compound) such as a diyl group or a pyrazine-2,3-diyl group may be used.

  Further, it may be a group that meets and links heteroatoms such as an alkylimino group, a dialkylsilanediyl group, or a diarylgermandiyl group.

  By using the compound represented by the general formula (10), an organic EL device with higher luminous efficiency can be obtained. Furthermore, it can be set as a longer life organic EL element.

In the compounds represented by the general formula (11) to the general formula (15), the substituents represented by R ₁ and R ₂ are the substituents represented by R ₁₀₁ in the general formula (1). At the same time as the group.

In the general formula (15), examples of the 6-membered aromatic heterocyclic ring each containing at least one nitrogen atom represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ include a pyridine ring and a pyridazine ring. , Pyrimidine ring, pyrazine ring and the like.

In the general formula (16), examples of the 6-membered aromatic heterocycle each containing at least one nitrogen atom represented by Z ₁ and Z ₂ include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Etc.

In the general formula (16), the arylene groups represented by Ar ₁ and Ar ₂ include o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, and pyrenediyl group. Group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group, kinkphenyldiyl group, sexi Examples thereof include a phenyldiyl group, a septiphenyldiyl group, an octylphenyldiyl group, a nobiphenyldiyl group, and a deciphenyldiyl group. The arylene group may further have a substituent described later.

In the general formula (16), the divalent aromatic heterocyclic groups represented by Ar ₁ and Ar ₂ are furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzo Imidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, And divalent groups derived from a ring in which the carbon atom of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic group may have a substituent represented by R ₁₀₁ .

In the general formula (16), the divalent linking group represented by L has the same meaning as the divalent linking group represented by L ₁ in the general formula (10), but is preferably an alkylene group. , —O—, —S— and the like, are divalent groups containing a chalcogen atom, most preferably an alkylene group.

In the general formula (17), in Ar _1, Ar _2, the arylene group represented by each, in the general formula (16), is synonymous with the arylene group represented by each of Ar _1, Ar _2.

In the general formula (17), an aromatic heterocyclic group represented by each of Ar _1, Ar _2, in the general formula (16), the divalent aromatic heterocyclic ring represented by each of Ar _1, Ar ₂ Synonymous with group.

In the general formula (17), examples of the 6-membered aromatic heterocycle each containing at least one nitrogen atom represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ include a pyridine ring and a pyridazine ring. , Pyrimidine ring, pyrazine ring and the like.

In the general formula (17), the divalent linking group represented by L has the same meaning as the divalent linking group represented by L ₁ in the general formula (10), but is preferably an alkylene group. , —O—, —S— and the like, are divalent groups containing a chalcogen atom, most preferably an alkylene group.

  Although the specific example of a compound represented by General formula (1) based on this invention below is shown, this invention is not limited to these.

  Although the typical synthesis example of the compound based on this invention is shown below, this invention is not limited to these.

  << Synthesis of Exemplified Compound 73 >>

  To a mixed solution obtained by adding 6.87 g of 4,4′-diiodobiphenyl and 6.00 g of β-carboline in 50 ml of N, N-dimethylacetamide, 4.5 g of copper powder and 7.36 g of potassium carbonate were added for 15 hours. Heated to reflux. After allowing to cool, water chloroform was added, and insolubles were removed by filtration. The organic layer was separated, washed with water and saturated brine, and concentrated under reduced pressure. The obtained residue was dissolved in acetic acid, treated with activated carbon, and recrystallized to give 4.2 g of colorless crystals of Exemplified Compound 73. Got.

The structure of Exemplified Compound 73 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The physical property data and spectrum data of the exemplified compound 73 are shown below.

Colorless crystals, melting point 200 ° C
MS (FAB) m / z: 487 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.3-7.5 (m, 2H), 7.5-7.6 (m, 4H), 7.7-7.8 (m, 4H), 7.9-8.0 (m, 4H), 8.06 (d, J = 5.1 Hz, 2H), 8.24 (d, J = 7.8 Hz, 2H), 8.56 ( d, J = 5.1 Hz, 2H), 8.96 (s, 2H)
<< Synthesis of Exemplary Compound 74 >>

  0.32 g of palladium acetate and 1.17 g of tri-tert-butylphosphine were dissolved in 10 ml of anhydrous toluene, 50 mg of sodium borohydride was added, and the mixture was stirred at room temperature for 10 minutes, then δ-carboline 5.00 g, 4, 4 5.87 g of '-diiodobiphenyl and 3.42 g of sodium tert-butoxide were dispersed in 50 ml of anhydrous xylene and stirred at reflux temperature for 10 hours under a nitrogen atmosphere. The resulting reaction mixture was allowed to cool, chloroform and water were added to separate the organic layer, the organic layer was washed with water and saturated brine, and then concentrated under reduced pressure. The resulting residue was dissolved in tetrahydrofuran. After the activated carbon treatment, 5.0 g of colorless crystals of Exemplified Compound 74 was obtained by recrystallization.

The structure of exemplary compound 74 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The physical property data and spectrum data of the exemplified compound 74 are shown below.

MS (FAB) m / z: 487 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.37 (dd, J = 4.7 Hz, J = 8.3 Hz, 2H), 7.4-7.5 (m, 2H), 7. 5-7.6 (m, 4H), 7.7-7.8 (m, 4H), 7.81 (dd, J = 1.2 Hz, J = 8.3 Hz, 2H), 7.9-8 0.0 (m, 4H), 8.48 (d, J = 7.8 Hz, 2H), 8.65 (dd, J = 1.2 Hz, J = 4.6 Hz, 2H)
<< Synthesis of Exemplary Compound 60 >>

  To a mixed solution in which 6.87 g of 4,4′-diiodobiphenyl and 6.00 g of γ-carboline were added to 50 ml of N, N-dimethylacetamide, 4.5 g of copper powder and 7.36 g of potassium carbonate were added for 15 hours. Heated to reflux. After allowing to cool, water chloroform was added, and insolubles were removed by filtration. The organic layer was separated, washed with water and saturated brine, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography and crystallized in dichloromethane / cyclohexane to give colorless crystals of Exemplified Compound 60. 4.3 g was obtained.

The structure of the exemplary compound 60 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The physical property data and spectrum data of the exemplary compound 60 are shown below.

MS (FAB) m / z: 487 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.4-7.4 (m, 4H), 7.4-7.5 (m, 4H), 7.7-7.8 (m, 4H) 7.9-8.0 (m, 4H), 8.25 (d, J = 7.8 Hz, 2H), 8.57 (d, J = 5.6 Hz, 2H), 9.42 (s) , 1H)
<< Synthesis of Exemplary Compound 144 >>

  0.16 g of palladium acetate and 0.58 g of tri-tert-butylphosphine are dissolved in 10 ml of anhydrous toluene, 25 mg of sodium borohydride is added and stirred for 10 minutes at room temperature, then 2.00 g of δ-carboline, intermediate a3 20 g and 1.37 g of sodium tert-butoxide were dispersed in 50 ml of anhydrous xylene and stirred at reflux temperature for 10 hours under a nitrogen atmosphere. After allowing to cool, chloroform and water are added to separate the organic layer. The organic layer is washed with water and saturated brine and then concentrated under reduced pressure. The resulting residue is recrystallized from acetic acid to give colorless colorless compound of Exemplified Compound 144. 1.5 g of crystals were obtained.

The structure of exemplary compound 144 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The spectrum data of the exemplary compound 144 are as follows.

MS (FAB) m / z: 647 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 1.80 (S, 12H), 7.27 (S, 4H), 7.34 (dd, J = 4.9 Hz, J = 8.3 Hz, 2H ), 7.3-7.4 (m, 2H), 7.4-7.5 (m, 12H), 7.76 (dd, J = 1.3 Hz, J = 8.3 Hz, 2H), 8 .45 (d, J = 7.8 Hz, 2H), 8.63 (dd, J = 1.3 Hz, J = 4.9 Hz, 2H)
<< Synthesis of Exemplary Compound 143 >>

  Add 4,5'-dichloro-3,3'-bipyridyl 0.85 g, diamine b 0.59 g, dibenzylideneacetone palladium 44 mg, imidazolium salt 36 mg, sodium tert-butoxide 1.09 g to 5 ml dimethoxyethane, 80 The mixture was stirred at 24 ° C. for 24 hours. After allowing to cool, chloroform and water were added to separate the organic layer, and the organic layer was washed with water and saturated brine and then concentrated under reduced pressure. The obtained residue was recrystallized from ethyl acetate to give Example Compound 143. 0.3 g of colorless crystals was obtained.

The structure of the exemplary compound 143 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The spectrum data of the exemplary compound 143 are shown below.

MS (FAB) m / z 639 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ): δ / ppm 7.46 (d, J = 5.7 Hz, 4H), 7.6-7.7 (m, 4H), 7.8-7.9 ( m, 4H), 8.67 (d, J = 5.7 Hz, 4H), 9.51 (S, 4H)
<< Synthesis of Exemplary Compound 145 >>
In the synthesis of Exemplified Compound 143, the same procedure was carried out except that one pyridine ring of 4,4'-dichloro-3,3'-bipyridyl was changed to benzene and 3- (2-chlorophenyl) -4-chloropyridine was used. Example compound 145 was synthesized.

The structure of exemplary compound 145 was confirmed by ¹ H-NMR spectrum and mass spectrometry spectrum. The spectrum data of the exemplary compound 145 are shown below.

MS (FAB) m / z 637 (M + ¹ )
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 7.3-7.4 (m, 2H), 7.6-7.7 (m, 4H), 7.7-7.8 (m, 4H) ) 7.8-7.9 (m, 4H), 8.06 (d, J = 5.3 Hz, 2H), 8.23 (d, J = 7.8 Hz, 2H), 8.56 (d, J = 5.3 Hz, 2H), 8.96 (S, 2H)
In addition to the above synthesis examples, the azacarbazole rings and chloroplasts of these compounds are described in J. Org. Chem. Soc. Perkin Trans. 1, 1505-1510 (1999), Pol. J. et al. Chem. , 54, 1585 (1980), (Tetrahedron Lett. 41 (2000), 481-484). Introduction of the synthesized azacarbazole ring or its chloroplast to the core or linking group of an aromatic ring, a heterocyclic ring, an alkyl group, etc. is known such as Ullman coupling, coupling using Pd catalyst, Suzuki coupling, etc. This method can be used.

  The compound according to the present invention preferably has a molecular weight of 400 or more, more preferably 450 or more, still more preferably 600 or more, and particularly preferably a molecular weight of 800 or more. Thereby, the glass transition temperature is raised, the thermal stability is improved, and the life can be further extended.

  The compound represented by the general formula (1) according to the present invention is used as a hole blocking material in a hole blocking layer which is a constituent layer of an organic EL element described later. However, from the viewpoint of controlling various physical properties of the organic EL element, the compound represented by the general formula (1) according to the present invention may be used for other constituent layers of the organic EL element.

<< Compound Represented by Formula (A) >>
The compound represented by the general formula (A) according to the present invention will be described.

In the general formula (A), the substituent represented by R ₂₁ has the same meaning as the substituent represented by R ₁₀₁ in the general formula (1).

<< Compound Represented by Formula (B) >>
The compound represented by the general formula (B) according to the present invention will be described.

In the general formula (B), as the arylene group represented by Ar ₃₁ and Ar ₃₂ , o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, Naphthylnaphthalenediyl group, biphenyldiyl group (for example, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl Group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group and the like.

These groups may further have a substituent represented by R ₁₀₁ in the general formula (1).

In the general formula (B), examples of the divalent heterocyclic group represented by Ar ₃₁ and Ar ₃₂ include an oxazolediyl group, a pyrimidinediyl group, a pyridazinediyl group, a pyrandiyl group, a pyrrolinediyl group, an imidazolinediyl group, Examples include imidazolidinediyl group, pyrazolidinediyl group, pyrazolinediyl group, piperidinediyl group, piperazinediyl group, morpholinediyl group, quinuclidinediyl group, thiophene-2,5-diyl group, pyrazine- A divalent linking group derived from a compound having an aromatic heterocyclic ring (also referred to as a heteroaromatic compound) such as a 2,3-diyl group may be used.

These groups may further have a substituent represented by R ₁₀₁ in the general formula (1).

In the general formula (B), each of R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ is the same as the substituent represented by R ₁₀₁ in the general formula (1).

In the general formula (B), examples of the divalent linking group represented by L ₃ include hydrocarbon groups such as alkylene groups, alkenylene groups, alkynylene groups, and arylene groups, as well as the alkylene groups, the alkenylene groups, and the alkynylenes. Group and the arylene group may each contain a heteroatom (for example, a nitrogen atom, a sulfur atom, a silicon atom, etc.), a thiophene-2,5-diyl group, a pyrazine-2,3- It may be a divalent linking group derived from a compound having an aromatic heterocyclic ring (also called a heteroaromatic compound) such as a diyl group, or may be a chalcogen atom such as oxygen or sulfur. Moreover, the group connected through a hetero atom, such as an alkylimino group, a dialkylsilanediyl group or a diarylgermandiyl group, may be used.

In the general formula (B), examples of the alkylene group used as the divalent linking group represented by L ₃ include an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, and the like. Methylene group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group) Etc.), cyclopentylene group (for example, 1,5-cyclopentanediyl group, etc.) and the like.

In the general formula (B), examples of the alkenylene group used as the divalent linking group represented by L ₃ include a propenylene group, a vinylene group (also referred to as an ethynylene group), and a 4-propyl-2-pentenylene group. Can be mentioned.

In the general formula (B), examples of the alkynylene group used as the divalent linking group represented by L ₃ include an ethynylene group and a 3-pentynylene group.

In the general formula (B), the arylene group used as the divalent linking group represented by L ₃ includes an o-phenylene group, an m-phenylene group, a p-phenylene group, a naphthalenediyl group, an anthracenediyl group, and a naphthacenediyl group. Group, pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group, kinkphenyldiyl group , A sexiphenyldiyl group, a septiphenyldiyl group, an octiphenyldiyl group, a nobiphenyldiyl group, a deciphenyldiyl group, and the like.

In the general formula (B), examples of the divalent heterocyclic group used as the divalent linking group represented by L ₃ include an oxazolediyl group, a pyrimidinediyl group, a pyridazinediyl group, a pyrandiyl group, and a pyrrolindiyl group. Imidazoline diyl group, imidazolidine diyl group, pyrazolidine diyl group, pyrazoline diyl group, piperidine diyl group, piperazine diyl group, morpholine diyl group, quinuclidine diyl group and the like, and thiophene-2,5-diyl Or a divalent linking group derived from a compound having an aromatic heterocycle (also referred to as a heteroaromatic compound) such as a pyrazine-2,3-diyl group.

In the general formula (B), examples of the trivalent linking group represented by L ₃ include ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, and octant. Riyl group, nonanetriyl group, decanetriyl group, undecanetriyl group, dodecanetriyl group, cyclohexanetriyl group, cyclopentanetriyl group, benzenetriyl group, naphthalenetriyl group, triazinetriyl group, etc. Further, those in which one divalent linking group is further attached to each of the above divalent linking groups can be used as the trivalent group.

Further, each of the divalent or trivalent linking group represented by L ₃ may be further substituted with a substituent represented by R ₁₀₁ in the general formula (1).

<< Compound Represented by Formula (C) >>
The compound represented by formula (C) according to the present invention will be described.

In the general formula (C), the substituents represented by Ra to Rg have the same meaning as the substituent represented by R ₁₀₁ in the general formula (1).

<< Compound Represented by Formula (D) >>
The compound represented by the general formula (D) according to the present invention will be described.

In the general formula (D), examples of the aromatic hydrocarbon group represented by Ar ₅₁ and Ar ₅₂ include a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, Examples include an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, and a biphenylyl group.

These groups may further have a substituent represented by R ₁₀₁ in the general formula (1).

In the general formula (D), examples of the aromatic heterocyclic group represented by Ar ₅₁ and Ar ₅₂ include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzoimidazolyl group, a pyrazolyl group, and a pyrazinyl group. , Triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl Group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (composing carboline ring of carbonyl group) One of the carbon atoms replaced by a nitrogen atom), quinoxa Examples thereof include a linyl group, a pyridazinyl group, a triazinyl group, a quinazolinyl group, and a phthalazinyl group.

These groups may further have a substituent represented by R ₁₀₁ in the general formula (1).

  Hereinafter, although the specific compound example of the compound group which consists of said general formula (A)-(D) is given, this invention is not limited to these.

  The compound represented by the general formula (1) according to the present invention, the compounds represented by the general formulas (A) to (D), and the like are respectively organic EL element materials (backlight, flat panel display, illumination light source, Used for display elements, electrophotographic light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communication devices, etc.), but for other uses, materials for organic semiconductor lasers (recording) Light source, exposure light source, reading light source optical communication device, electrophotographic light source, etc.) electrophotographic photoreceptor material, organic TFT element material (organic memory element, organic arithmetic element, organic switching element), organic wavelength conversion element material It can be used in a wide range of fields such as materials for photoelectric conversion elements (solar cells, optical sensors, etc.).

  Next, the constituent layers of the organic EL device of the present invention will be described in detail.

In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.
(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode << Anode >>
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (100 μm or more) Degree), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc. / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal with a film thickness of 1-20 nm on a cathode, a transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

  Next, an injection layer, a blocking layer, an electron transport layer and the like used as the constituent layers of the organic EL element of the present invention will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. You may let them.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

<Blocking layer: hole blocking layer, electron blocking layer>
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, as described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization” (issued on November 30, 1998 by NTS Corporation). There is a hole blocking layer.

  The hole blocking layer is an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and blocks holes while transporting electrons. Thus, the probability of recombination of electrons and holes can be improved.

  The hole blocking layer of the organic EL device of the present invention is provided adjacent to the light emitting layer.

  In this invention, it is preferable to contain the compound which concerns on this invention mentioned above as a hole blocking material of a hole blocking layer. Thereby, it can be set as an organic EL element with much higher luminous efficiency. Furthermore, the lifetime can be further increased.

  On the other hand, the electron blocking layer is a hole transport layer in a broad sense, made of a material that has a function of transporting holes and has a very small ability to transport electrons, and blocks electrons while transporting holes. Thus, the probability of recombination of electrons and holes can be improved.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

(Host compound)
The light-emitting layer of the organic EL device of the present invention preferably contains the following host compound and phosphorescent compound (also referred to as a phosphorescent compound). Preference is given to using the compounds according to the invention. Thereby, the luminous efficiency can be further increased. Moreover, you may contain compounds other than the compound which concerns on said this invention as a host compound.

  Here, in the present invention, the host compound is defined as a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.01 at room temperature (25 ° C.) among compounds contained in the light emitting layer.

  Furthermore, a plurality of known host compounds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  As these known host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature) are preferable.

  Specific examples of known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Moreover, the light emitting layer may contain the host compound which has a fluorescence maximum wavelength further as a host compound. In this case, the energy transfer from the other host compound and the phosphorescent compound to the fluorescent compound allows electroluminescence as an organic EL element to be emitted from the other host compound having a fluorescence maximum wavelength. A host compound having a fluorescence maximum wavelength is preferably a compound having a high fluorescence quantum yield in a solution state. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more. Specific host compounds having a maximum fluorescence wavelength include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, and pyrylium dyes. Perylene dyes, stilbene dyes, polythiophene dyes, and the like. The fluorescence quantum yield can be measured by the method described in 362 (1992 edition, Maruzen) of Spectroscopic II of the Fourth Edition Experimental Chemistry Course 7.

(Phosphorescent compound (phosphorescent compound))
The material used for the light emitting layer (hereinafter referred to as the light emitting material) preferably contains a phosphorescent compound at the same time as the host compound. Thereby, it can be set as an organic EL element with higher luminous efficiency.

  The phosphorescent compound according to the present invention is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0.2 at 25 ° C. 01 or more compounds. The phosphorescence quantum yield is preferably 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the above phosphorescence quantum yield in any solvent.

  There are two types of light emission of phosphorescent compounds in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is phosphorescent. Energy transfer type to obtain light emission from the phosphorescent compound by transferring to the compound, the other is that the phosphorescent compound becomes a carrier trap, carrier recombination occurs on the phosphorescent compound, and from the phosphorescent compound In any case, the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.

  The phosphorescent compound used in the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum). Complex-based compounds) and rare earth complexes, most preferably iridium compounds.

  Although the specific example of a phosphorescent compound is shown below, this invention is not limited to these. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like.

  In the present invention, the phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited. In principle, the phosphorescent compound can be obtained by selecting a central metal, a ligand, a ligand substituent, and the like. However, it is preferable that the phosphorescent compound has a maximum phosphorescence emission wavelength of 380 nm to 480 nm. With such a blue phosphorescent organic EL element and a white phosphorescent organic EL element, the luminous efficiency can be further increased.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Minolta) is applied to the CIE chromaticity coordinates.

  The light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5 nm-200 nm. The light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are composed of one or more kinds, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Good.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbenes Derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers, and the like can be given.

  As the hole transport material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as an electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and similarly to the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC can be used. A semiconductor can also be used as an electron transport material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

<Substrate>
The organic EL device of the present invention is preferably formed on a substrate.

  The substrate (hereinafter also referred to as a substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc. Although there is no restriction | limiting in particular, As a board | substrate used preferably, glass, quartz, and a transparent resin film can be mentioned, for example. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples include films made of triacetate (TAC), cellulose acetate propionate (CAP), and the like. On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed.

  The external extraction efficiency at room temperature for light emission of the organic electroluminescence device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a thin film made of a desired electrode material, for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode. To do. Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are organic EL element materials, is formed thereon.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When employing the vapor deposition film, the deposition conditions may vary due to kinds of materials used, generally boat temperature 50 ° C. to 450 ° C., vacuum degree 10- ⁶ Pa~10- ² Pa, deposition rate 0 It is desirable to select appropriately within the range of 0.01 nm / second to 50 nm / second, substrate temperature −50 ° C. to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 nm to 200 nm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL element is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  The multicolor display device of the present invention is provided with a shadow mask only when the light emitting layer is formed, and the other layers are common, so that patterning of the shadow mask or the like is not necessary. A film can be formed by a method or a printing method.

  When patterning is performed only on the light emitting layer, the method is not limited. However, a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The display device of the present invention can be used as a display device, a display, and various light emission sources. In a display device or a display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  The lighting device of the present invention includes home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light sensors Although a light source etc. are mentioned, it is not limited to this.

  Further, the organic EL element according to the present invention may be used as an organic EL element having a resonator structure.

  Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.

<Display device>
The organic EL element of the present invention may be used as one kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using three or more organic EL elements of the present invention having different emission colors. Alternatively, it is possible to make one color emission color, for example, white emission, into BGR by using a color filter to achieve full color. Furthermore, it is possible to convert the emission color of the organic EL to another color by using a color conversion filter, and in this case, λmax of the organic EL emission is preferably 480 nm or less.

  An example of a display device composed of organic EL elements will be described below with reference to the drawings.

  FIG. 1 is a schematic diagram illustrating an example of a display device including organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. The pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below. FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at orthogonal positions (details are shown in FIG. Not shown).

  When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data. Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 3 is a schematic diagram of a pixel.

  The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

  That is, the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.

  The potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 4 is a schematic view of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal. In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

  The organic EL material according to the present invention can also be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. As a combination of a plurality of luminescent colors, those containing three luminescence maximum wavelengths of three primary colors of blue, green, and blue may be used. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescent or phosphorescent light, and the light emission. Any combination of a dye material that emits light from the material as excitation light may be used, but in the white organic electroluminescence device according to the present invention, a method of combining a plurality of light-emitting dopants is preferable.

  As a layer structure of an organic electroluminescence device for obtaining a plurality of emission colors, a method of having a plurality of emission dopants in one emission layer, a plurality of emission layers, and an emission wavelength in each emission layer And a method of forming minute pixels emitting light having different wavelengths in a matrix.

  In the white organic electroluminescence device according to the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like at the time of film formation, if necessary. When patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.

  The light emitting material used for the light emitting layer is not particularly limited. For example, in the case of a backlight in a liquid crystal display element, the platinum complex according to the present invention is known so as to be suitable for the wavelength range corresponding to the CF (color filter) characteristics. Any one of the light emitting materials may be selected and combined to be whitened.

  As described above, the light-emitting organic EL element of the present invention that emits white light is used as a kind of lamp such as a home lighting, an interior lighting, and an exposure light source as various light emitting sources and lighting devices in addition to the display device and the display. Further, it is also useful for display devices such as backlights for liquid crystal display devices.

  Others such as backlights for watches, billboard advertisements, traffic lights, optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. There are a wide range of uses such as household appliances.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
<< Production of Organic EL Element 1-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was placed in a molybdenum resistance heating boat, and 200 mg of H-8 as a host compound was placed in another molybdenum resistance heating boat, Put 200 mg of bathocuproin (BCP) in another molybdenum resistance heating boat, put 100 mg of Ir-12 in another resistance heating boat made of molybdenum, and put 200 mg of Alq ₃ in another resistance heating boat made of molybdenum. Installed.

Next, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is heated by heating, vapor-deposited on a transparent support substrate at a vapor deposition rate of 0.1 nm / second, and hole transport A layer was provided. Further, the heating boat containing H-8 and Ir-12 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively, to obtain a light emitting layer. Was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature. Furthermore, the heating boat containing BCP was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer. Further, the heating boat containing Alq ₃ is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-15 >>
In the production of the organic EL device 1-1, H-8 used as the host compound of the light emitting layer is replaced with the organic EL device material shown in Table 1 to be used as a host compound, and BCP used as a hole blocking compound is shown. 1-2 to 1-15 were produced in the same manner as the organic EL element 1-1 except that the hole transport material shown in 1 was used.

<< Evaluation of Organic EL Elements 1-1 to 1-15 >>
The following evaluation was performed about obtained organic EL element 1-1 to 1-15.

《External extraction quantum efficiency》
The produced organic EL device was measured for external extraction quantum efficiency (%) when a constant current of ^2.5 mA / cm ² was applied at 23 ° C. in a dry nitrogen gas atmosphere. For the measurement, a spectral radiance meter CS-1000 (manufactured by Minolta) was used.

"lifespan"
When driving at a constant current of ^2.5 mA / cm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured, and this was calculated as the half-life time (
It was used as an index of life as τ0.5). For the measurement, spectral radiance meter CS-100
0 (Minolta) was used.

  Moreover, the measurement results of the external extraction quantum efficiency and lifetime in Table 1 are expressed as relative values when the measured value of the organic EL element 1-1 is 100.

  From Table 1, it is clear that the organic EL device of the present invention is superior in both external quantum efficiency and lifetime as compared with the comparison.

Example 2
<< Preparation of Organic EL Element 2-1 >>
In the production of the organic EL element 1-1 of Example 1, an organic EL element 2-1 was produced in the same manner except that the dopant compound of the light emitting layer was changed to Ir-1.

<< Production of Organic EL Elements 2-2 to 2-15 >>
Subsequently, in the production of the organic EL element 2-1, H-8 used as the host compound of the light emitting layer is replaced with a material for the organic EL element shown in Table 2 to be used as a host compound and used as a hole blocking compound. Organic EL devices 2-2 to 2-15 were produced in the same manner except that the compounds shown in Table 2 were used instead of BCP.

  About each of obtained organic EL element 2-1 to 2-15, it carried out similarly to the description in Example 1, and measured and evaluated the external extraction quantum efficiency and lifetime. Moreover, the measurement results of the external extraction quantum efficiency and lifetime in Table 2 were expressed as relative values when the measured value of the organic EL element 2-1 was 100.

  The obtained results are shown in Table 2.

  From Table 2, it is clear that the organic EL device of the present invention is superior in both external quantum efficiency and lifetime as compared with the comparison.

Example 3: (Example of lighting device, using white organic EL element)
In the organic EL element 2-2 produced in Example 2, the same as the organic EL element 2-2 except that Ir-1 used in the light emitting layer was changed to a mixture of Ir-1, Ir-9, and Ir-12. The organic EL element 2-2W produced by the method was used. The non-light emitting surface of the organic EL element 2-2W was covered with a glass case to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life. FIG. 5 is a schematic view of the lighting device, and FIG. 6 is a cross-sectional view of the lighting device. The organic EL element 101 is covered with a glass cover 102 and connected with a power line (anode) 103 and a power line (cathode) 104. 105 is a cathode and 106 is an organic EL layer. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 7 Power supply line 10 Organic EL element 11 Switching transistor 12 Drive transistor 13 Capacitor A Display part B Control part 107 Glass substrate with a transparent electrode 106 Organic EL layer 105 Cathode 102 Glass cover 103 Power supply line ( anode)
104 Power line (cathode)
108 Nitrogen gas 109 Water catching agent

Claims (25)

In the organic electroluminescence device having at least a light emitting layer and a hole blocking layer as a constituent layer,
The hole blocking layer contains a compound represented by the following general formula (1), and the light emitting layer is at least one selected from the group of compounds consisting of the following general formula (B) or general formula (C). An organic electroluminescence device comprising a seed compound.

[ Wherein , Z ₁ represents a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring or triazine ring , Z ₂ represents a benzene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring or triazine ring , and Z ₃ represents It represents —CH ₂ —, —O— , —S— or a simple bond. R ₁₀₁ represents a hydrogen atom or a substituent. ]

[In the formula, Ar ₃₁ and Ar ₃₂ each represent an arylene group or a divalent heterocyclic group, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a substituent, and L ₃ represents a divalent linkage. Represents a group, a trivalent linking group or a single bond. n31, n32, n33, and n34 each represent an integer of 0 to 4, and n3 represents 1 or 2. However, the compound shown below is excluded from the compound represented by the general formula (B). ]

[Wherein, Ra to Rg each represents a hydrogen atom or a substituent, and the substituents represented by Ra to Rg may be the same or different. m represents an integer of 1 to 3, and n represents an integer of 0 to 2. However, the compound shown below is remove | excluded from the compound represented by this general formula (C). ]

In the general formula (1) , Z ₁ represents a pyridine ring, Z ₂ represents a benzene ring or a pyridine ring, Z ₃ represents a simple bond, and the light emitting layer is composed of the general formula (B). The organic electroluminescence device according to claim 1, comprising at least one compound selected from the group of compounds . The organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (1-3).

[In the formula, R ₅₂₁ ~ R ₅₂₇ Each independently represents a hydrogen atom or a substituent. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (1-4).

[In the formula, R ₅₃₁ ~ R ₅₃₇ Each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (1-5).

[In the formula, R ₅₄₁ ~ R ₅₄₈ Each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (1-6).

[In the formula, R ₅₅₁ ~ R ₅₅₈ Each independently represents a hydrogen atom or a substituent. ] The organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (1-9).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ] The organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (1-10).

[Wherein, R represents a hydrogen atom or a substituent. The plurality of R may be the same or different. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (3).

[In the formula, R ₆₀₁ ~ R ₆₀₆ Each independently represents a hydrogen atom or a substituent, ₆₀₁ ~ R ₆₀₆ At least one represents at least one group selected from the groups represented by the general formulas (2-1) to (2-4), and R ₅₀₂ ~ R ₅₀₇ , R ₅₁₂ ~ R ₅₁₇ , R ₅₂₂ ~ R ₅₂₇ , R ₅₃₂ ~ R ₅₃₇ Each independently represents a hydrogen atom or a substituent, and the substituents may be the same or different. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (4).

[In the formula, R ₆₁₁ ~ R ₆₂₀ Each independently represents a hydrogen atom or a substituent, ₆₁₁ ~ R ₆₂₀ At least one represents at least one group selected from the groups represented by formulas (2-1) to (2-4) according to claim 9. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (7).

[In the formula, R ₆₅₁ ~ R ₆₅₆ Each independently represents a hydrogen atom or a substituent, ₆₅₁ ~ R ₆₅₆ At least one represents at least one group selected from the groups represented by formulas (2-1) to (2-4) according to claim 9. na represents an integer of 0 to 5, and nb represents an integer of 1 to 6, but the sum of na and nb is 6. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (10).

[In the formula, R ₆₉₁ ~ R ₇₀₀ Each independently represents a hydrogen atom or a substituent, ₁ Represents a divalent linking group. R ₆₉₁ ~ R ₇₀₀ At least one represents at least one group selected from the groups represented by formulas (2-1) to (2-4) according to claim 9. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (11).

[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (12).

[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (13).

[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (14).

[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (15).

[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom or a substituent. n and m each represent an integer of 1 to 2, and k and l each represent an integer of 3 to 4. However, n + k = 5 and l + m = 5. Z ₁ , Z ₂ , Z ₃ , Z ₄ Each represents a 6-membered aromatic heterocycle containing at least one nitrogen atom. ] The organic electroluminescence device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (16).

[Wherein, o and p each represent an integer of 1 to 3; Ar ₁ , Ar ₂ Each represents an arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ Represents a 6-membered aromatic heterocyclic ring each containing at least one nitrogen atom, and L represents a divalent linking group. ] The organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the general formula (1) is represented by the following general formula (17).

[Wherein, o and p each represent an integer of 1 to 3; Ar ₁ , Ar ₂ Each represents a divalent arylene group or a divalent aromatic heterocyclic group. Z ₁ , Z ₂ , Z ₃ , Z ₄ Represents a 6-membered aromatic heterocyclic ring each containing at least one nitrogen atom, and L represents a divalent linking group. ] The phosphorescent light-emitting layer is included as the constituent layer, and the phosphorescent light-emitting layer contains the compound represented by the general formula (1). Organic electroluminescence element. A display device comprising the organic electroluminescence element according to claim 1. The organic electroluminescence device according to any one of claims 1 to 20, wherein the light emission is white. A display device comprising the organic electroluminescence element according to claim 22. An illuminating device comprising the organic electroluminescent element according to claim 22. A display device comprising the illumination device according to claim 24 and a liquid crystal element as a display means.

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